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Cathodoluminescenceand depth
profiles of tin in float glass
B Yangt,
2. Experimental details
Measurements were made on float glass samples from
both Societa Italiana Vetro (SIV) and from Pilkington
plc. Since the luminescence signals were very similar,
only the data from SIV glass are reported here. The
samples were cut into 10 x 10 mm2 pieces and cleaned
1757
0022-3727/94/081757+6$19.50
B Yang et a/
1.5301
1.5281
X
1.5281
4
0
.k
1.5211
&
2 1.5281
1.5251
0. 0
2.00
4.00
d o
Depth (Microns)
36000
30000
41
\
6000
.-._
.---______
300
400
500
6 o
700
Wavelength (nm)
aoo
900
B Yang et a/
26000,
30000
._..._..SLOW coomc
FAST COOLlNG
ROOK TEMPEKATURE
20000
2
380nm
575nm
.
0
0
Wavelength (nm)
5b
Id0
150
200
250
300
Temperature (K)
I
04
zoo
I
.',
zoo
,?'--
ddo
.500
I
so0
760
Wavelength (nm)
abo
d o
4. Discussion
The immediately obvious feature from figure 1 is that
the independent monitors of the effects of tin diffusion,
namely via the refractive index and the longwavelength
CL provide the same depth profile. One can thus
attribute such changes to the penetration of tin into
the glass. The data suggest that there is a saturation
region near the surface followed by a Gaussian-type
diffision tail extending down to some 8 p m depth.
Intuitively this is a reasonable consequence of the float
process. However one should note that the analyses
are on a relatively coarse depth scale and thus smaller
scale variations are smoothed over. Earlier analyses of
the depth concentration of the Sn 17-11] using SIMS,
RBS, Auger and Mossbauer techniques are not totally
consistent. They generally show an overall pattern of a
decreasing concentration with depth, but in some cases
there are indications of a peak in the concentration close
to the surface (atdepths of, say, 100 nm). Such subtleties
are not resolvable by the current techniques.
In order to analyse the luminescence data one should
note that the SIV glass contains more than 70% silica, and
some alkali and alkaline earth oxides, e.g. NazO, CaO
and MgO. For such a glass the atomic structure has a
short-range regular arrangement of atoms but a complete
lack of any long-range periodicity and regularity. The
block is the most important
silica tetrahedron
molecular building unit and the glass lattice network is
fomed from such units, but the oxygen ions may also be
linked to an alkali metal or an alkaline-earth metal ion.
The intrinsic emission from the silicate group has been
studied in many types of sample, including such diverse
examples as silica and quartz, silica fibres, feldspars
and zircon (e.g. see reviews in [4,12-141). Despite
the wide selection of host structnres there are many
similarities with a general pattern of blue/UV emission
in the wavelength range 300 to 380 nm, which is
variously ascribed to intrinsic luminescenceemitted from
relaxed self-trapped excitons decaying at the intrinsic
(SO4) site, or wavelength shifted variations of this
recombination resulting from the presence of defects
such as the intrinsic examples of E or E, centres, or from
common impurities such as H, Al or Ge. Consequently,
for the present data, the assumption is that the emission
bands near 380 nm and 410 nm in the blue end of the
spectrum of this silicate glass are similarly related to
intrinsic electron hole recombination. In some of the
samples the 380 nm signal was more pronounced after
heat treatment. Since there are considerable variations
in the assignments of the origin of the defects which
produce luminescence, even at the same wavelength,
table 1 lists some of the more common interpretations.
CL is not a passive probe of the defect sites and,
whilst changes in energy obviously sample different
depths of material, variations in current at the same
electron beam energy may alter the relative intensities
of different emission bands. In part this is because
for an insulator the secondary electron emission and
space charge development induce a complex electric
(nm)
(eV)
Method
Possible model
260
290
370
380
390
400
450-480
470
570
580
640
4.77
4.28
3.78
3.25
3.17
3.1
2.5-2.8
2.64
2.18
2.15
1.9
CL
pL,cL,n
Oxygen vacancy
Oxygen vacancy
RbTL,
Ha04
RL
PL,TL
RL,CL
w,n
A104
a,cL,n
CL
CL
CL.16
Ge impurity
Oxygen vacancy
Na impurity
B Yang et a1
12000
Acknowledgments
4000
2oooj
0
,,io
o.io
040
0.60
0.40
0.50
0.60
0.70
temperature.
of the glass but on the float side the changes were
minimal, implying that at the high tin dopant levels the
glass had reached a saturation equilibrium. This view is
confirmed by the refractive index data where the index
is constant for nearly 3 pm into the glass.
5. Conclusion
1762
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